US8663736B2 - Germanium complexes with amidine derivative ligand and process for preparing the same - Google Patents
Germanium complexes with amidine derivative ligand and process for preparing the same Download PDFInfo
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- US8663736B2 US8663736B2 US13/143,621 US201013143621A US8663736B2 US 8663736 B2 US8663736 B2 US 8663736B2 US 201013143621 A US201013143621 A US 201013143621A US 8663736 B2 US8663736 B2 US 8663736B2
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- 239000003446 ligand Substances 0.000 title abstract description 16
- 150000001409 amidines Chemical class 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title description 3
- 150000002290 germanium Chemical class 0.000 title description 2
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 143
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 143
- 239000000126 substance Substances 0.000 claims abstract description 51
- 239000010409 thin film Substances 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 13
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 13
- -1 alkali metal salt Chemical class 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 229910052783 alkali metal Inorganic materials 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical group CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 10
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 46
- 239000000203 mixture Substances 0.000 description 18
- 238000000151 deposition Methods 0.000 description 16
- 238000002411 thermogravimetry Methods 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 0 [1*]N1C(C)[NH+]([2*])[GeH2-]1C Chemical compound [1*]N1C(C)[NH+]([2*])[GeH2-]1C 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- 230000008021 deposition Effects 0.000 description 13
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 125000001309 chloro group Chemical group Cl* 0.000 description 9
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 9
- RHIUIXSTQSQFAX-UHFFFAOYSA-N lithium ethyl(methyl)azanide Chemical compound [Li+].CC[N-]C RHIUIXSTQSQFAX-UHFFFAOYSA-N 0.000 description 9
- NYMJLNHIEKAQSD-UHFFFAOYSA-N dichlorogermanium;1,4-dioxane Chemical compound Cl[Ge]Cl.C1COCCO1 NYMJLNHIEKAQSD-UHFFFAOYSA-N 0.000 description 8
- 238000004455 differential thermal analysis Methods 0.000 description 8
- YDGSUPBDGKOGQT-UHFFFAOYSA-N lithium;dimethylazanide Chemical compound [Li+].C[N-]C YDGSUPBDGKOGQT-UHFFFAOYSA-N 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910000618 GeSbTe Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- ZYOFLPFKBVINPE-UHFFFAOYSA-N CC(C)N1C(C)[NH+](C(C)C)[GeH2-]1N(C)C.CC(C)N1C(N(C)C)[NH+](C(C)C)[GeH2-]1C(C)(C)C.CC(C)N1C(N(C)C)[NH+](C(C)C)[GeH2-]1N(C)C.CCN(C)C1N(C(C)C)[GeH2-](N(C)CC)[NH+]1C(C)C.CCN(C)[GeH2-]1N(C(C)C)C(C)[NH+]1C(C)C.CCN(C)[GeH2-]1N(C(C)C)C(N(C)C)[NH+]1C(C)C Chemical compound CC(C)N1C(C)[NH+](C(C)C)[GeH2-]1N(C)C.CC(C)N1C(N(C)C)[NH+](C(C)C)[GeH2-]1C(C)(C)C.CC(C)N1C(N(C)C)[NH+](C(C)C)[GeH2-]1N(C)C.CCN(C)C1N(C(C)C)[GeH2-](N(C)CC)[NH+]1C(C)C.CCN(C)[GeH2-]1N(C(C)C)C(C)[NH+]1C(C)C.CCN(C)[GeH2-]1N(C(C)C)C(N(C)C)[NH+]1C(C)C ZYOFLPFKBVINPE-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000000427 thin-film deposition Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- OXTURSYJKMYFLT-UHFFFAOYSA-N dichlorogermane Chemical compound Cl[GeH2]Cl OXTURSYJKMYFLT-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910000078 germane Inorganic materials 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- NQNBJQNVAGAKCG-UHFFFAOYSA-N CC(C)N1C(N(C)C)[NH+](C(C)C)[GeH2-]1N(C)C.CCN(C)C1N(C(C)C)[GeH2-](N(C)CC)[NH+]1C(C)C Chemical compound CC(C)N1C(N(C)C)[NH+](C(C)C)[GeH2-]1N(C)C.CCN(C)C1N(C(C)C)[GeH2-](N(C)CC)[NH+]1C(C)C NQNBJQNVAGAKCG-UHFFFAOYSA-N 0.000 description 1
- 229910006111 GeCl2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QUZPNFFHZPRKJD-UHFFFAOYSA-N germane Chemical compound [GeH4] QUZPNFFHZPRKJD-UHFFFAOYSA-N 0.000 description 1
- QHGIKMVOLGCZIP-UHFFFAOYSA-N germanium dichloride Chemical compound Cl[Ge]Cl QHGIKMVOLGCZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052986 germanium hydride Inorganic materials 0.000 description 1
- IMJFOQOIQKIVNJ-UHFFFAOYSA-N germanium(2+) Chemical compound [Ge+2] IMJFOQOIQKIVNJ-UHFFFAOYSA-N 0.000 description 1
- CULSIAXQVSZNSV-UHFFFAOYSA-N germanium(4+) Chemical compound [Ge+4] CULSIAXQVSZNSV-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- MUDDKLJPADVVKF-UHFFFAOYSA-N trichlorogermane Chemical compound Cl[GeH](Cl)Cl MUDDKLJPADVVKF-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/30—Germanium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
Definitions
- the present invention relates to a novel germanium complex with an amidine derivative ligand and a method for preparing the same, more preferably to preparation of an asymmetric germanium complex useful as a precursor for preparing germanium thin film or germanium-containing compound thin film.
- germanium precursors are used in silicon-germanium solar cells, optical coatings, or the like. Recently, they are used in various fields including the manufacture of GeSbTe (GST) thin film as next-generation semiconductor device.
- GST GeSbTe
- germane In general, germane (GeH 4 ) is used as a germanium precursor in producing germanium thin film or germanium-containing compound thin film. Germane is toxic gas in standard condition and is difficult to handle. Therefore, it needs safety equipment for process application. In addition, it is restricted in use in semiconductor processes requiring low temperature, since a deposition temperature of about 500° C. or higher is necessary for chemical vapor deposition (CVD). For other organometallic germanium precursors, those with alkyl (R), alkoxy (OR) or cyclopentadiene (Cp) groups as ligand are reported.
- organometallic germanium precursors those with alkyl (R), alkoxy (OR) or cyclopentadiene (Cp) groups as ligand are reported.
- US Patent Application No. 2003/0111013 discloses deposition methods of silicon germanium layer for thin film preparation using mono-, di-, tri- or tetrachlorogermane. However, these compounds are not appropriate for deposition of germanium because they are decomposed at low temperature.
- Korean Patent Application No. 2007-0042805 discloses a method for preparing a germanium(II) complex with an aminoalkoxide ligand. This compound is a liquid material which is decomposed approximately at 236° C.
- PCT/US2007/063830 discloses deposition methods of GST thin film using a germanium precursor with an alkylamino ligand
- Korean Patent Application No. 2004/0112906 discloses deposition methods of GST thin film using a germanium(IV) precursor with a silylamino ligand.
- the inventors of the present invention have developed a new asymmetric germanium precursor with an amidine derivative ligand, having improved thermal stability and being capable of deposition at low temperature.
- An object of the present invention is to provide a novel asymmetric germanium complex and a method for preparing the same. Another object of the present invention is to provide a method for preparing germanium thin film by using novel germanium complex capable of deposition at low temperature of below 300° C.
- the present invention relates to a germanium complex represented by Chemical Formula 1.
- Y 1 and Y 2 are independently selected from R 3 , NR 4 R 5 or OR 6 , and R 1 through R 6 independently represent (C 1 -C 7 )alkyl.
- the germanium complex according to the present invention is thermally stable, is highly volatile, and does not include halogen components. Therefore, it may be usefully used as a precursor to produce high-quality germanium thin film or germanium-containing compound thin film by metal organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD).
- MOCVD metal organic chemical vapor deposition
- ALD atomic layer deposition
- Y 1 and Y 2 may be independently selected from —N(CH 3 ) 2 , —N(CH 3 )(CH 2 CH 3 ), —CH 3 , or —C(CH 3 ) 3 , and R 1 through R 2 may independently represent methyl, ethyl, propyl or t-butyl.
- Y 1 and Y 2 may be the same ligand, but, more preferably, Y 1 and Y 2 may be different ligands.
- germanium complex represented by Chemical Formula 1 may be selected from the following structures:
- the germanium complex represented by Chemical Formula 1 according to the present invention may have various substituents introduced to the amidine ligand binding with the central metal germanium thus to control steric hindrance. As a result, intermolecular interaction may be reduced and the total molecular weight may be controlled thus to increase volatility.
- Such a structural characteristic provides the germanium complex according to the present invention with the following advantages.
- the germanium complex exists as liquid at room temperature, is highly soluble in organic solvents such as benzene, tetrahydrofuran, toluene, etc., and has good volatility. Accordingly, the germanium complex according to the present invention may be very useful as a precursor to produce germanium thin film or germanium-containing compound thin film.
- the germanium complex represented by Chemical Formula 1 according to the present invention may be prepared by a method commonly used in the related art. Although not particularly limited thereto, the present invention provides the following preparation method.
- a germanium complex may be prepared by a method comprising:
- M 1 and M 2 independently represent an alkali metal
- Y 1 and Y 2 are independently selected from R 3 , NR 4 R 5 or OR 6
- R 1 through R 6 independently represent (C 1 -C 7 )alkyl.
- Chemical Formula 1 may be rewritten as Chemical Formula 7.
- germanium complex represented by Chemical Formula 7 may be selected from the following structures:
- the germanium complex represented by Chemical Formula 7 may be prepared by the following preparation method.
- the present invention provides a method for preparing a germanium complex, comprising:
- M 1 represents an alkali metal
- Y 1 is selected from R 3 , NR 4 R 5 or OR 6
- R 1 through R 6 independently represent (C 1 -C 7 )alkyl.
- germanium(II) halide may be Ge(II)Br 2 , Ge(II)Cl 2 (dioxane) or Ge(II)I 2 .
- M 1 and M 2 may be independently lithium, sodium or potassium, more preferably lithium, and Y 1 and Y 2 may be independently —N(CH 3 ) 2 , —N(CH 3 )(CH 2 CH 3 ), —CH 3 or —C(CH 3 ) 3 .
- alkylcarbodiimide (R 1 NCNR 2 ) represented by Chemical Formula 4 may be 1,3-diisopropylcarbodiimide.
- the germanium complex according to the present invention may be prepared by Scheme 1.
- M 1 represents an alkali metal
- Y 1 is selected from R 3 , NR 4 R 5 or OR 6
- R 1 through R 6 independently represent (C 1 -C 7 )alkyl.
- the germanium complex according to the present invention may also be prepared by Scheme 2.
- Y 2 may be represented by Y 1 .
- the complex represented by Chemical Formula 5 and a germanium(II) halide (GeX 2 (dioxane)) are added and reacted at low temperature, for example at ⁇ 70° C., to obtain the germanium complex represented by Chemical Formula 7.
- This reaction may be carried out by stirring for 8 to 14 hours after adding the germanium(II) halide.
- the organic solvent that may be used in the present invention includes ether, hexane, toluene, etc.
- germanium(II) halide GeX 2 (dioxane) may be Ge(II)Br 2 , Ge(II)Cl 2 (dioxane) or Ge(II)I 2 .
- M 1 , Y 1 , R 1 and R 2 are the same as described above.
- 1 molar equivalent of the alkali metal salt represented by Chemical Formula 3 is reacted with 1 molar equivalent of the alkylcarbodiimide represented by Chemical Formula 4 at low temperature, for example at ⁇ 70° C., to obtain the complex represented by Chemical Formula 5.
- the step b) of the preparation method of the present invention may be carried out according to Scheme 4 and Scheme 5.
- M 1 and M 2 independently represent an alkali metal
- Y 1 and Y 2 are independently selected from R 3 , NR 4 R 5 or OR 6
- R 1 through R 6 independently represent (C 1 -C 7 )alkyl.
- prepared germanium complex according to the present invention may be liquid at room temperature, and T 1/2 (the temperature at which the weight of the sample reaches 1 ⁇ 2 of the original weight) in the thermogravimetric analysis (TGA) may be from 140 to 190° C.
- TGA thermogravimetric analysis
- the structure of the germanium complex may be identified by nuclear magnetic resonance spectroscopy (NMR) or elemental analysis (EA).
- the present invention further provides a method for preparing a germanium thin film, comprising: injecting the germanium complex represented by Chemical Formula 1 to a substrate provided in a reactor to prepare a germanium thin film by chemical vapor deposition (CVD) or ALD (atomic layer deposition).
- CVD chemical vapor deposition
- ALD atomic layer deposition
- the temperature of the substrate may range from 150 to 350° C.
- the substrate may be a silicon monocrystalline substrate or other semiconductor substrate. More specifically, a TiN/SiO 2 /Si substrate may be used.
- the germanium thin film may be prepared using a reaction gas.
- the reaction gas may be oxygen, hydrogen, ammonia gas, etc., but is not limited thereto.
- the inflow rate of the reaction gas may vary depending on the thin film to be deposited.
- the deposition pressure may range from 3 to 5 torr, but is not particularly limited thereto.
- the germanium complex with an amidine derivative according to the present invention has an asymmetric structure, exists as transparent liquid at room temperature, and may be easily obtained from a pure compound through vacuum distillation.
- the germanium complex with an amidine derivative according to the present invention is thermally stable, is highly volatile, and does not include halogen components. Therefore, it may be usefully used as a precursor to produce high-quality germanium thin film or germanium-containing compound thin film by metal organic chemical vapor deposition (MOCVD) or atomic layer deposition (ALD).
- MOCVD metal organic chemical vapor deposition
- ALD atomic layer deposition
- the germanium complex according to the present invention may have various substituents introduced to the amidine ligand binding with the central metal germanium thus to control steric hindrance.
- intermolecular interaction may be reduced and the total molecular weight may be controlled thus to increase volatility.
- germanium complex is pyrolyzable at low temperature in the absence of a reducing agent, it may be advantageously utilized as a precursor to produce high-quality germanium thin film or germanium-containing compound thin film.
- FIG. 1 shows X-ray diffraction (XRD) analysis result of the germanium thin films deposited in Example 7 and Example 9 according to the present invention.
- FIG. 2 shows X-ray photoelectron spectroscopy (XPS) analysis result of the germanium thin films deposited in Example 7 and Example 9 according to the present invention.
- XPS X-ray photoelectron spectroscopy
- FIG. 3A shows scanning electron microscopy (SEM) analysis result of the germanium thin film deposited in Example 7
- FIG. 3 B shows SEM analysis result of the germanium thin film deposited in Example 8
- FIG. 3 C shows SEM analysis result of the germanium thin film deposited in Example 9.
- FIG. 4 shows proton nuclear magnetic resonance spectroscopy ( 1 H NMR) analysis result of the germanium complex prepared in Example 1.
- FIG. 5 shows 1 H NMR analysis result of the germanium complex prepared in Example 3.
- FIG. 6 shows 1 H NMR analysis result of the germanium complex prepared in Example 4.
- FIG. 7 shows thermogravimetric analysis (TGA) and differential thermal analysis (DTA) results of the germanium complex prepared in Example 1.
- FIG. 8 shows TGA and DTA results of the germanium complex prepared in Example 3.
- FIG. 9 shows TGA and DTA results of the germanium complex prepared in Example 5.
- TGA thermogravimetric analysis
- lithium ethylmethylamide solution anhydrous n-hexane (50 mL) and ethylmethylamine (LiNEtMe, 1.40 g, 23.70 mmol) were added to another 250 mL Schlenk flask. The mixture was cooled to ⁇ 70° C. and, after slowly adding n-butyllithium 2.5 M solution (9.48 mL, 23.70 mmol) dropwise, slowly warmed to room temperature and stirred for 4 hours to prepare lithium ethylmethylamide solution (solution I). The previously synthesized (N,N′-diisopropyl-dimethylguanidyl)(chloro)germanium was cooled to ⁇ 70° C. and slowly added dropwise to thus prepared lithium ethylmethylamide solution (solution I). The mixture was slowly warmed to room temperature and stirred for 12 hours.
- N,N′-diisopropyl-dimethylguanidyl)ethylmethylamino)germanium(II) was subjected to TGA.
- T 1/2 was 166° C.
- the N,N′-diisopropyl-dimethylguanidyl)(ethylmethylamino)germanium(II) was subjected to 1 H NMR analysis. The result is shown in FIG. 5 .
- TGA and DTA results are shown in FIG. 8 .
- dichlorogermanium-dioxane 7 g, 30.22 mmol
- anhydrous ether 100 mL
- lithium ethylmethylamide solution anhydrous n-hexane (50 mL) and ethylmethylamine (1.40 g, 23.70 mmol) were added to another 250 mL Schlenk flask and cooled to ⁇ 70° C.
- n-butyllithium 2.5 M solution 9.48 mL, 23.70 mmol
- the mixture was slowly warmed to room temperature and stirred for 4 hours to prepare lithium ethylmethylamide.
- the previously synthesized (N,N′-diisopropyl-methylamidyl)(chloro)germanium was cooled to ⁇ 70° C.
- a germanium thin film was formed by metal organic chemical vapor deposition (MOCVD) using the (N,N′-diisopropyl-dimethylguanidyl)(dimethylamino)germanium(II) synthesized in Example 1 as source material and using argon as carrier gas.
- the (N,N′-diisopropyl-dimethylguanidyl)(dimethylamino)germanium(II) was carried to a TiN/SiO 2 /Si substrate inside a chamber at about 50 sccm using argon as the carrier gas.
- the source temperature was maintained at about 60° C., and the substrate temperature at 300° C. Deposition was carried out for 1 hour. Deposition pressure was maintained at 3 torr.
- X-ray diffraction (XRD) analysis result of thus deposited germanium thin film is shown in FIG. 1 , X-ray photoelectron spectroscopy (XPS) analysis result shown in FIG. 2 , and scanning electron microscopy (SEM) analysis result in FIG. 3 A).
- the thin film had a thickness of about 1 ⁇ m.
- Deposition was carried out in a similar manner as Example 7, except that the substrate temperature was maintained at 250° C.
- Deposition was carried out in a similar manner as Example 7, except that the substrate temperature was maintained at 200° C.
- FIG. 1 XRD analysis result of thus deposited germanium thin film is shown in FIG. 1 , XPS analysis result shown in FIG. 2 , and SEM analysis result in FIG. 3 C).
- the germanium thin film prepared according to the present invention was an amorphous germanium thin film.
- the XPS analysis result of FIG. 2 shows that thin film deposition could be accomplished in Example 9. Accordingly, it was confirmed that the germanium complex according to the present invention could be deposited to form a thin film even at a relatively low temperature of 200° C.
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US20130330911A1 (en) * | 2012-06-08 | 2013-12-12 | Yi-Chiau Huang | Method of semiconductor film stabilization |
CN105849221B (en) * | 2013-09-27 | 2019-06-18 | 乔治洛德方法研究和开发液化空气有限公司 | The trimethylsilyl amine and three-dimethylamino silane ylamine compounds that amine replaces |
CN106068335A (en) * | 2014-03-04 | 2016-11-02 | 皮考逊公司 | Germanium or the ald of germanium oxide |
JP6306386B2 (en) * | 2014-03-20 | 2018-04-04 | 株式会社日立国際電気 | Substrate processing method, substrate processing apparatus, and program |
US9911916B2 (en) * | 2014-03-28 | 2018-03-06 | Hitach, Ltd. | Method for vapor-phase growth of phase-change thin film, and device for vapor-phase growth of phase-change thin film |
KR102139285B1 (en) * | 2016-09-30 | 2020-07-30 | 주식회사 한솔케미칼 | Organometallic precursor compound for vapor deposition for forming oxide thin film and method for manufacturing same |
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